Method for reducing pattern dimension in photoresist layer

ABSTRACT

The invention discloses improvements in the so-called coated thermal flow process for reducing the pattern dimension of a patterned resist layer on a substrate to accomplish increased fineness of resist patterning, in which a coating layer of a water-soluble resin formed on the patterned resist layer is heat-treated to effect thermal shrinkage of the coating layer with simultaneous reduction of the pattern dimension followed by removal of the coating layer by washing with water. The improvement of the process is obtained by using an aqueous coating solution admixed with a water-soluble amine compound such as triethanolamine in addition to a water-soluble resin such as a polyacrylic acid-based polymer. Further improvements can be obtained by selecting the water-soluble resin from specific copolymers including copolymers of (meth)acrylic acid and a nitrogen-containing monomer such as N-vinylpyrrolidone, N-vinylimidazolidinone and N-acryloylmorpholine as well as copolymers of N-vinylpyrrolidone and N-vinylimidazolidinone in a specified copolymerization ratio.

BACKGROUND OF THE INVENTION

[0001] The present invention relates to improvements in a method forobtaining a patterned photoresist layer of which the resist pattern hasa reduced dimension by a post-patterning heat treatment. Moreparticularly, the invention relates to improvements in the method forreducing the pattern dimension in a photolithographically patternedresist layer by a post-patterning procedure in which a patterned resistlayer on a substrate is provided thereon with a coating layer of awater-soluble resin and then the thus coated patterned resist layer issubjected to a heat treatment to effect thermal shrinkage of the resistlayer resulting in a reduced pattern dimension followed by completeremoval of the coating layer of the water-soluble resin by washing withwater.

[0002] Along with the recent trend in the technology of semiconductordevices toward higher and higher degrees of integration and more andmore compact sizes of the devices, the photolithographic patterningtechnology of photoresist layers is also required to accomplish finerand finer patterning of the photoresist layer.

[0003] An approach for accomplishing the above mentioned requirement inthe photolithographic technology for a pattern dimension of 0.20 μm orfiner is to use a patterning exposure light of very short wavelengthssuch as KrF excimer laser beams, ArF excimer laser beams and F₂ excimerlaser beams as well as electron beams. This approach, however, cannot besuccessful without development of a photoresist composition havingadaptability to these short-wavelength exposure radiations.

[0004] In this regard, so-called chemical-amplification photoresistcompositions are widely employed in the modern photolithographictechnology, in which the catalytic activity of an acid generated in thelight-exposed areas from a radiation-sensitive acid-generating agentcontained in the resist layer is utilized to effect a solubility changeof the resinous ingredient to give high sensitivity and patternresolution even with a small amount of the acid-generating agent.

[0005] As a method for obtaining very finely patterned resist layer on asubstrate, there is a known method in which a photoresist layer formedon a substrate is patterned in a conventional way including patterninglight-exposure and development and the thus patterned resist layer isprovided with a coating layer of a resin by utilizing the activity ofthe acid diffused from the resist layer followed by a heat treatment soas to effect reduction of the pattern dimension to be finer than theresolution limit inherent in the photoresist composition (JapanesePatent Kokai 5-166717 and 5-241348).

[0006] This method, however, has a problem in respect of the relativelylarge temperature dependency amounting to more than 10 nm/° C. withinthe substrate surface. This disadvantage can hardly be overcome with theheating device currently employed in the manufacture of semiconductordevices due to poor uniformity of the temperature distribution.Accordingly, the above-described method of post-patterningdimension-reducing method cannot be practiced without substantialvariations in the pattern dimensions.

[0007] It is also known that the dimension of a patterned resist layercan be reduced below the resolution limit of the photoresist compositionby subjecting the patterned resist layer to a heat treatment or aradiation irradiation treatment to cause mobilization of the patternedresist layer. Though advantageous in respect of small temperaturedependency of only a few nm/° C. within the plane of the substratesurface, this method has a problem that, due to the difficulty incontrolling mobilization of the photoresist layer by the heat treatment,uniform reduction of the dimension of the photoresist layer can hardlybe expected within the substrate surface.

[0008] Besides the above described photolithographic patterning processby utilizing excimer laser beams for patterning light exposure,proposals are made in Japanese Patent No. 2723260 for reduction of thepattern dimension, according to which a layer of an electron beam resistcomposition comprising a polymethyl methacrylate resin is patterned togive a patterned resist layer which is then provided thereon with acoating layer of a positive-working resist composition followed by aheat treatment to form a reacted layer at the interface between thepatterned resist layer and the positive-working resist layer and removalof the positive-working resist layer from the unreacted areas. JapanesePatent Kokai 6-250379 further discloses a method in which a reactedlayer is formed between the underlying patterned resist layer and theupper resist layer by utilizing the acid generated from theacid-generating agent or thermal crosslinking by the acid. JapanesePatent Kokai 10-73927 discloses a method for the manufacture ofsemiconductor devices by effecting reduction of the pattern dimension inwhich the overcoating layer is formed by using, as the coating solution,a composition prepared by dissolving a water-soluble resin,water-soluble crosslinking agent or combination thereof in awater-miscible solvent without addition of any photosensitiveingredients. Japanese Patent Kokai 2000-347414 proposes a method inwhich a substrate surface is provided thereon with a photosensitivelayer of a chemical-amplification photoresist composition which issubjected to patterning light-exposure and development to form apatterned resist layer, a coating film is formed on the patterned resistlayer by using a coating composition containing a water-soluble resinsuch as a polyvinyl acetal, water-soluble crosslinking agent such astetra(hydroxymethyl)glycoluril, a water-soluble nitrogen-containingcompound such as amines and, optionally, a fluorine- andsilicon-containing surface active agent followed by a heat treatment toform a water-insoluble reacted layer at the interface between thepatterned resist layer and the overcoating layer and finally theovercoating layer in the unreacted areas is removed by using a solvent.

[0009] Although each of the above-described methods is desirable becausereduction of the pattern dimension can be conveniently accomplished toexceed the wavelength limitation of the photoresist composition byforming an upper coating layer on the underlying photoresist layer,several disadvantages are involved therein. For example, thecrosslinking reaction of the overcoating composition may overly proceedto unnecessary portions such as the bottom of the patterned resist layerresulting in an undesirable non-orthogonal cross sectional profilethereof eventually with trailing skirts. The dimension of the upperresist layer depends on the mixing baking which is a heat treatment tocause crosslinking. Further, the temperature dependency obtained bythese methods is relatively large to be 10 nm/° C. or larger so that itis very difficult to ensure high uniformity of the pattern dimensionwithin the substrate surface when the substrate has a large size or thepatterned resist layer is extremely fine resulting in poorcontrollability in reduction of the pattern dimension.

[0010] Besides, a proposal is made in Japanese Patent Kokai 1-307228 and4-364021 for the so-called thermal flow process in which a patternedphotoresist layer formed on a substrate is subjected to a heat treatmentor radiation-irradiation treatment to effect mobilization of the resistlayer so as to accomplish reduction of the pattern dimension to becomefiner than the resolution limit of the photoresist composition.

[0011] This method, however, is defective because products ofreproducible quality can hardly be obtained due to the difficultyencountered in controlling the mobility of the resist by means of heator radiation. As a further development of this thermal flow process,Japanese Patent Kokai 7-45510 proposes a method in which the mobility ofthe resist is controlled by providing a coating layer of a water-solubleresin on the patterned photoresist layer formed on a substrate. Sincethe water-soluble resin used in this method, such as polyvinyl alcohols,is insufficient in the solubility in water required in the removal withwater and long-term stability, troubles are sometimes caused by theresidual resin film remaining unremoved with water.

SUMMARY OF THE INVENTION

[0012] In view of the above described problems and disadvantages in theprior art, the present invention has an object to provide an improvementin the method for reducing the dimension of a patterned photoresistlayer by a post-patterning treatment in which the patterned resist layeris provided thereon with a coating layer of a water-soluble resincomposition followed by a heat treatment to cause reduction of thepattern dimension or the distance between the resist patterns and thenremoval of the water-soluble coating layer away from the patternedresist layer by washing with water.

[0013] Thus, in a first aspect of the invention, the present inventionprovides, in a method for reducing a pattern dimension in a patternedphotoresist layer formed on a substrate by a post-patterning heattreatment, referred to as the coated thermal flow process hereinafter,comprising the steps of: (a) forming a coating layer of a water-solubleresin composition on the patterned resist layer, (b) drying the coatinglayer of the aqueous coating solution, (c) subjecting the dried coatinglayer and the patterned resist layer to a heat treatment to effectthermal shrinkage of the patterned resist layer with reduction of thepattern dimension and (d) removing the coating layer of thewater-soluble resin composition, the improvement which comprises: using,in step (a), a coating solution containing a water-soluble resin and awater-soluble amine compound having, preferably, a pKa value of 7.5 to13.0 at 25° C. for the formation of the coating layer.

[0014] In a second aspect of the invention, the improvement provided bythe present invention comprises, in step (a) of the coated thermal flowprocess, using an aqueous coating solution containing a water-solubleresin which is a copolymer of (A) acrylic acid, methacrylic acid or acombination thereof and (B) a water-soluble ethylenically unsaturatedcompound which is exemplified by N-vinylpyrrolidone,N-vinylimidazolidinone, methyl acrylate, methyl methacrylate,N,N-dimethylacrylamide, N, N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, N-methhylacrylamide,diacetoneacrylamide, N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate,N-acryloylmorpholine and the like, of which those nitrogen-containingwater-soluble compounds are preferable, or a combination thereof.

[0015] In a third aspect of the invention, the present invention isdirected to an improvement of the aqueous coating solution for use instep (a) of the coated thermal flow process in which the water-solubleresin is a copolymer of N-vinylpyrrolidone and a water-soluble monomericvinyl compound other than N-vinylpyrrolidone which is preferablyN-vinylimidazolidinone.

[0016] In a fourth aspect of the invention, the present inventionprovides, in the above-mentioned coated thermal flow process of apatterned resist layer, the improvement which comprises, as a guidelinefor the selection of the water-soluble resin in step (a) of the methodusing an aqueous coating solution containing a water-soluble resinexhibiting such a water-solubility behavior that, in a testing procedurecomprising the steps of forming a coating layer of the resin on anunpatterned photocured layer of the photoresist composition, subjectingthe coating layer to a heat treatment at 140° C. for 60 seconds andremoving away the coating film by washing with water at 23° C., thecoating layer can be completely removed within 60 seconds.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention provides, according to the first aspect ofthe invention, an improvement in the formulation of the aqueous coatingsolution used for the formation of a water-soluble coating layer on apatterned photoresist layer in step (a) of the so-called coated thermalflow process, in which the coating layer and the patterned resist layerare subjected to a heat treatment, for example, at 80 to 160° C. for 30to 90 seconds followed by complete removal of the coating layer bywashing with water. The temperature of this heat treatment shouldpreferably be lower than the softening point of the patterned resistlayer. When the heat treatment is conducted at such a temperature, thepatterned resist layer receives a tension from the coating layer to givemore remarkable reduction in the dimension of holes and trenches with adecrease in the dependency on the duty ratio, i.e. the line distancewithin the plane of substrate surface. The above-mentioned softeningpoint of the resist layer is a temperature at which, when the patternedresist layer formed on a substrate is gradually heated, an incipientspontaneous flow of the mobilized resist layer is detected.

[0018] The water-soluble resin contained in the aqueous coating solutionused in the coated thermal flow process is not particularly limitativeand can be selected from a variety of water-soluble polymers includingalkyleneglycol-based polymers, cellulosic polymers, vinyl polymers,acrylic polymers, urea-based polymers, epoxy polymers, melamine-basedpolymers and polyamide polymers. Although any of these water-solublepolymers can be used either singly or as a combination of two kinds ormore, it is preferable in respect of the efficiency for reduction of thepattern distance without affecting the cross sectional profile of thepatterned resist layer that the water-soluble resin is a homopolymer ofan acrylic monomer or a copolymer of an acrylic monomer with othercopolymerizable monomers.

[0019] Examples of the above-mentioned acrylic monomer include acrylicacid, methyl acrylate, methacrylic acid, methyl methacrylate, N,N-dimethyl acrylamide, N, N-dimethylaminopropyl methacrylamide,N,N-dimethylaminopropyl acrylamide, N-methyl acrylamide, diacetoneacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethylmethacrylate, N,N-dimethylaminoethyl acrylate and N-acryloylmorpholine.

[0020] Examples of the comonomer compound copolymerized with the abovenamed acrylic monomers include vinyl monomers such asN-vinylpyrrolidone, N-vinylimidazolidinone, vinyl acetate and the like.

[0021] The aqueous coating solution used in step (a) of the coatedthermal flow process is prepared by dissolving one or a combination ofthe above named water-soluble resins in water in a concentration of 3 to50% by weight or, preferably, 5 to 20% by weight. When the concentrationis too low, the coating layer formed from the coating solution issometimes incomplete while, when the concentration is too high, thedesired effect of the coated thermal flow process can little beaccomplished.

[0022] According to the first aspect of the invention, the aqueouscoating solution as described above is further admixed with awater-soluble amine compound which, preferably, has a pKa value of 7.5to 13.0 at 25° C. Examples of suitable amine compounds includealkanolamines such as monoethanolamine, diethanolamine, triethanolamine,2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine,N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylehtanolamine,N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine,monoisopropanolamine, diisopropanolamine, triisopropanolamine and thelike, polyalkylene polyamines such as diethylenetriamine,triethylenetetramine, propylenediamine, N,N′-diethylethylenediamine,1,4-butanediamine, N-ethylethylenediamine, 1,2-propanediamine,1,3-propanediamine, 1,6-hexanediamine and the like, aliphatic aminessuch as 2-ethylhexylamine, dioctylamine, tributylamine, tripropylamine,triallylamine, heptylamine, cyclohekylamine and-the like, aromaticamines such as benzylamine, diphenylamine and the like and cyclic aminessuch as piperazine, N-methylpiperazine, methylpiperazine,hydroxyethylpiperazine and the like. These amine compounds can be usedeither singly or as a combination of two kinds or more. It ispreferable, however, that the water-soluble amine compound has a boilingpoint of 140° C. or higher under normal pressure in order not to be lostby the heat treatment of the coating layer. In this regard,monoethanolamine and triethanolamine are suitable.

[0023] The amount of the water-soluble amine compound added to theaqueous coating solution is in the range from 0.1 to 30% by weight or,preferably, from 2 to 15% by weight based on the amount of thewater-soluble resin. When the amount of the amine compound is too small,the aqueous coating solution eventually suffers a decrease in storagestability due to degradation. When the amount exceeds 30% by weight, inparticular, an adverse effect is caused on the cross sectional profileof the patterned resist layer. The problem of denaturation of theaqueous coating solution can be at least partly solved by admixing thecoating solution with an acidic compound such as p-toluene sulfonic acidand dodecylbenzene sulfonic acid. The coating layer can be imparted withincreased stability by admixing the aqueous coating solution with asurface active agent.

[0024] In the method according to the first aspect of the presentinvention, the patterned resist layer formed on a substrate is coated atleast partly with the above described aqueous coating solution followedby drying to give a dried coating layer and then subjected to a heattreatment which can be conducted in substantially the same manner as inthe conventional thermal flow process. Namely, the patterned resistlayer is coated with the coating solution of the water-soluble resin byusing a coating machine such as a spinner and the coating layer is driedby heating at about 80 to 160° C. for 30 to 90 seconds. It is optionalthat the patterned resist layer coated with the water-soluble resin issubjected beforehand to a pre-baking treatment at 80 to 100° C. for 30to 90 seconds. The concentration of the water-soluble resin in theaqueous coating solution is in the range from 3 to 50% by weight or,preferably, from 5 to 20% by weight depending on the desired thicknessof the coating layer which is in the range from 0.1 to 0.5 μm.

[0025] The aqueous solvent used in the above-described aqueous coatingsolution is usually water but it is optional that the solvent is amixture of water with a water-miscible alcoholic solvent such as methylalcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, glycerin,ethyleneglycol, propyleneglycol, 1,2-butyleneglycol, 1,3-butyleneglycoland 2,3-butyleneglycol. These water-miscible alcoholic solvents can beadded to water in a mixing proportion not exceeding 30% by weight basedon water.

[0026] According to the first aspect of the invention, reduction of theresist pattern dimension accomplished by the coated thermal flow processcan be to such an extent that the width of a trench pattern is decreasedfrom 220 nm to 160 nm and the diameter of a hole pattern is decreasedfrom 180 nm to 160 nm. After the thus accomplished thermal shrinkage ofthe patterned resist layer, the coating layer of the water-soluble resinformed thereon is completely removed by washing for 10 to 60 secondswith an aqueous solvent which is preferably water.

[0027] A finely patterned resist layer formed by the photolithographictechnology can be imparted in this way with an increased fineness of thepattern dimension to exceed the resolution limit accomplished in aconventional process without affecting other characteristics requiredfor the finely patterned resist layer.

[0028] According to the second aspect of the invention, the presentinvention provides an aqueous coating solution for use in the coatedthermal flow process, of which the water-soluble resin is a copolymerconsisting of the monomeric units comprising (A) the monomeric unitsderived from acrylic acid, methacrylic acid or a combination of acrylicand methacrylic acids and (B) the monomeric units derived from variouskinds of ethylenically unsaturated monomeric compounds named beforeincluding, as preferable ones, N-vinylpyrrolidone,N-vinylimidazolidinone, N-acryloylmorpholine or a combination thereof ina molar ratio of (A):(B) in the range from 4:1 to 1:1. It is preferablethat the molar fraction of the monomeric units (A) is larger than thatof the units (B). Though not particularly limitative, it is preferablein respect of good film-forming behavior that the above-mentioned binarycopolymeric resin has a weight-average molecular weight in the rangefrom 10000 to 50000 as measured by the gel permeation chromatographicmethod making reference to polymethyl methacrylate resins having knownmolecular weights.

[0029] While the coating solution used in step (a) of the inventivemethod is basically an aqueous solution of the aforementionedwater-soluble copolymeric resin, it is optional that the aqueoussolution further contains water-soluble resins of other types in alimited amount including cellulose derivatives, alkyleneglycol-basedpolymers, urea-based polymers and melamine-based polymers.

[0030] The cellulose derivative mentioned above is exemplified byhydroxypropyl methyl cellulose phthalate, hydroxypropyl methyl celluloseacetate phthalate, hydroxypropyl methyl cellulose hexahydrophthalate,hydroxypropyl methyl cellulose acetate succinate, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, celluloseacetate hexahydrophthalate, carboxylmethyl cellulose, ethyl celluloseand methyl cellulose. The alkyleneglycol-based copolymer is exemplifiedby addition-polymerized polymers and copolymers of ethyleneglycol,propyleneglycol, butyleneglycol and the like. The urea-based polymer isexemplified by the polymers of methylolated urea, dimethylolated urea,ethyleneurea and the like. The melamine-based polymer is exemplified bythe polymers of methoxymethylated melamine, methoxymethylatedisobutoxymethylated melamine, methoxyethylated melamine and the like.Besides, epoxy-based polymers and amide-based polymers can also be used,if water-soluble. These water-soluble resins can be used either singlyor as a combination of two kinds or more.

[0031] The aqueous solvent used in the above-described aqueous coatingsolution is usually water but it is optional that the solvent is amixture of water with a water-miscible alcoholic solvent such as methylalcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, glycerin,ethyleneglycol, propyleneglycol, 1,2-butyleneglycol, 1,3-butyleneglycoland 2,3-butyleneglycol. These water-miscible alcoholic solvents can beadded to water in a mixing proportion not exceeding 30% by weight basedon water.

[0032] In the fine resist pattern-forming method according to theinvention, a desired fine resist pattern can be obtained with goodefficiency by successively undertaking the steps including: step (a2)for the formation of a resist pattern on a substrate; step (b2) for theformation of a coating layer of a water-soluble resin on the resistpattern; step (c2) for a heat treatment of the coating layer and step(d2) for the removal of the coating layer by washing with water each asdescribed below.

[0033] The step (a2) is a step for the formation of a resist pattern ona substrate by using a resist composition. In this step, which can beconducted according to a conventional photolithographic fine patterningprocedure in the manufacture of semiconductor devices, a substrate suchas a semiconductor silicon wafer is coated by spin coating with asolution of a chemical-amplification resist, electron beam resist or F₂laser beam resist to form a resist layer which is pattern-wise exposedto light through a photomask bearing a desired pattern or subjected toscanning with electron beams followed by a post-exposure bakingtreatment and then subjected to a development treatment with an aqueousalkaline solution as a developer such as a 1-10% by weight aqueoussolution of tetramethylammonium hydroxide to form the desired resistpattern.

[0034] The step (b2) is for the formation of a water-soluble resinouscoating layer on the resist pattern wholly or partially by using theabove-described aqueous coating solution of a water-soluble resin. Thecoating method can be the same as that under conventional use in thethermal flow process by using, for example, a spinner, if necessary,followed by heating for drying. The coating layer has a thickness,preferably, in the range from 0.1 to 0.5 μm.

[0035] The step (c2) is for a heat treatment of the resist patterncoated with a water-soluble resinous layer in step (b2) so as todecrease the distance between adjacent resist patterns. The heattreatment is conducted usually at a temperature of 80 to 160° C. for 30to 120 seconds. It is preferable that the heat treatment is conducted ata temperature lower than the softening point of the patterned resistlayer because the shrinkage rate of the resist pattern is free fromdependency on the duty ratio and fineness of holes and trenches can befurther increased by the attractive force exerted by the water-solubleresinous coating layer on the resist pattern. By this heat treatment, adecrease in the dimensions of the resist pattern can be obtained from220 nm to 160 nm for trenches and from 180 nm to 160 nm for holes.

[0036] In step (d2), the water-soluble coating layer covering the resistpattern after the heat treatment in step (c2) is removed by washing withan aqueous solvent or, preferably, deionized water. Removal of thecoating layer can be complete by washing usually for 10 to 60 seconds.

[0037] In essence, the present invention according to the second aspectof the invention also provides an improved coated thermal flow processin which the aqueous coating solution for the formation of a coatinglayer on a patterned resist layer contains the above defined copolymericresin as the resinous ingredient and the heat treatment of thewater-soluble coating layer is conducted at a temperature lower than thesoftening temperature of the patterned resist layer. While the abovementioned heat treatment of the coating layer is conducted usually at 80to 160° C. for 30 to 120 seconds, it is preferable that the heattreatment temperature is lower than the softening point of the patternedresist layer so that the patterned resist layer is subjected to tractionby the thermally shrinking coating layer to cause efficient reduction ofthe resist pattern dimension with a rate of shrinkage not depending onthe duty ratio.

[0038] According to the third aspect of the invention, the presentinvention provides an improved aqueous coating solution used in thecoated thermal flow process, in which the water-soluble resinousingredient contained in the aqueous coating solution is a copolymericresin consisting of the monomeric units comprising (A1) the monomericunits derived from N-vinylpyrrolidone and (B1) the monomeric unitsderived from a water-soluble monomeric vinyl compound other thanN-vinylpyrrolidone which is preferably N-vinylimidazolidinone in a molarratio of (A1):(B1) in the range from 1:9 to 9:1. Though not particularlylimitative, it is preferable in respect of good film-forming behaviorand heat resistance to withstand the heat treatment that theabove-mentioned binary copolymeric resin has a weight-average molecularweight in the range from 10000 to 50000 as measured by the gelpermeation chromatographic method making reference to polymethylmethacrylate resins having known molecular weights. The coated thermalflow process using the aqueous coating solution containing theabove-defined copolymeric resin is conducted in the same way as in thesecond aspect of the invention.

[0039] According to the fourth aspect of the invention, the improvementprovided by the present invention is related to a testing procedure forselection of the water-soluble resin as the solute in the aqueouscoating solution for the formation of a water-soluble coating layer on apatterned resist layer in the coated thermal flow process.

[0040] In practicing the solubility test of the water-soluble resin, acoating layer of the water-soluble resin is formed on an unpatterned butphotocured resist layer on a substrate and subjected to a heat treatmentat 140° C. for 60 seconds. Thereafter, the thus heat-treated coatinglayer of the water-soluble resin is washed with water at 23° C. todetermine the time taken for complete removal of the coating layer bydissolving away with water, which must be 60 seconds or shorter in orderfor the resin to be used in the coated thermal flow process according tothe present invention.

[0041] According to the above-described testing procedure for thesolubility behavior of the water-soluble resin, a polymeric resinselected from water-soluble acrylic polymers, vinyl polymers, cellulosederivatives, alkyleneglycol-based polymers, urea-based polymers,melamine-based polymers, epoxy-based polymers and amide-based polymerswhich passes the test can be used as the resinous ingredient in theaqueous coating solution. The solubility behavior of the water-solubleresin can be adjusted by copolymerizing the above-mentioned acrylicmonomer with a minor amount of comonomers of other types.

[0042] In the following, the present invention in various aspects isdescribed in more detail by way of Examples and Comparative Examples,which, however, never limit the scope of the invention in any way.

[0043] In the Examples and Comparative Examples described below, thewater-soluble resins as a solute in the aqueous coating solution weresubjected to a solubility test in the following manner. Thus, asemiconductor silicon wafer was uniformly coated on a spinner with achemical-amplification positive-working photoresist solution(TDUR-P036PM, a product by Tokyo Ohka Kogyo Co.) followed by a dryingheat treatment at 80° C. for 90 seconds to give a dried resist layerhaving a thickness of 0.7 μm. The resist layer was then coated uniformlywith an aqueous solution of the resin on test and the coating layer wassubjected to a heat treatment at 140° C. for 60 seconds to give acoating layer of 0.3 μm thickness. The substrate bearing the thusheat-treated coating layer was kept in water at 23° C. under vibrationto determine the length of time taken before complete dissolution andremoval of the coating layer. As a criterion, the water-soluble resinswere taken as acceptable when this dissolving took a time not exceeding60 seconds.

EXAMPLE 1

[0044] A semiconductor silicon wafer was uniformly coated on a spinnerwith a positive-working photoresist composition (TDUR-P036PM, a productby Tokyo Ohka Kogyo Co.) followed by a baking treatment at 80° C. for 90seconds to form a photoresist layer having a thickness of 560 nm.

[0045] The photoresist layer was subjected to a patterninglight-exposure treatment with KrF excimer laser beams on alight-exposure machine (Model Canon FPA-3000EX3, manufactured by CanonCo.) followed by a post-exposure baking treatment at 120° C. for 90seconds and then subjected to a development treatment with a 2.38% byweight aqueous solution of tetramethylammonium hydroxide to give a holepattern having a diameter of 182.3 nm.

[0046] In the next place, the resist layer having the thus formed holepattern was coated with a coating solution prepared by dissolving 9.1 gof a copolymeric resin of acrylic acid and N-vinylpyrrolidone in acopolymerization ratio of 2:1 by weight and 0.9 g of triethanolamine in90 g of water to form a coating layer which was subjected to a heattreatment at 120° C. for 60 seconds to cause thermal shrinkage followedby washing with water at 23° C. to dissolve away the coating layer. Theresult was that the coating layer could be completely removed by washingfor about 1 minute with a reduction of the hole pattern diameter to161.5 nm.

COMPARATIVE EXAMPLE 1

[0047] The experimental procedure was substantially the same as inExample 1 except that the coating solution was a 5% by weight aqueoussolution of a polyvinyl alcohol. The result obtained by washing away ofthe coating film with water was that visually recognizable residue ofthe coating layer was found.

EXAMPLE 2

[0048] A semiconductor silicon wafer was uniformly coated on a spinnerwith a positive-working photoresist composition (TDMR-AR2000, a productby Tokyo Ohka Kogyo Co.) followed by a pre-baking treatment at 90° C.for 90 seconds to form a photoresist layer having a thickness of 1.3 μm.

[0049] In the next place, the photoresist layer was subjected topatterning light exposure on an i-line light-exposure machine (ModelNikon NSR-2205i14E, manufactured by Nikon Co.) followed by apost-exposure baking treatment at 110° C. for 90 seconds and thensubjected to a development treatment to give a trench pattern of 411.1nm width.

[0050] The thus formed trench-patterned resist layer was provided in thesame manner as in Example 1 with a coating layer of the water-solubleresin followed by a heat treatment to effect thermal shrinkage and thenwashing away of the coating layer with water. The result was that thewidth of the trench pattern had been reduced from 411.1 nm to 219.5 nm.

EXAMPLE 3

[0051] The experimental procedure was substantially the same as inExample 1 except that the coating solution of a water-soluble resin wasprepared by dissolving, in 90 g of water, 9.5 g of a copolymeric resinof acrylic acid and N-vinylpyrrolidone in a copolymerization ratio of2:1 by weight and 0.5 g of monoethanolamine. The result was that thehole pattern diameter could be reduced from 182.3 nm to 160.3 nm.

EXAMPLE 4

[0052] A semiconductor silicon wafer was uniformly coated with apositive-working photoresist composition (EP-TF004EL, a product by TokyoOhka Kogyo Co.) on a spinner followed by a pre-baking treatment at 150°C. for 300 seconds to form a resist layer having a thickness of 2.0 μm.

[0053] The thus formed resist layer was pattern-wise irradiated byscanning electron beams on an electron-beam image tracing machine (ModelHITACHI HL800D50Kv, manufactured by Hitachi Ltd.) followed by apost-exposure baking treatment at 140° C. for 300 seconds and thensubjected to a development treatment with a 2.38% by weight aqueoussolution of tetramethylammonium hydroxide to give a trench-patternedresist layer having a trench width of 228.0 nm.

[0054] The thus trench-patterned resist layer was coated with the sameaqueous coating solution as used in Example 1 and the coating layer wassubjected to a heat treatment at 150° C. for 90 seconds to effectthermal shrinkage followed by washing away of the coating layer withwater to find that removal of the coating layer was complete afterwashing for about 60 seconds. The width of the trench pattern wasreduced from 228.0 nm to 155.0 nm.

EXAMPLE 5

[0055] A semiconductor silicon wafer was uniformly coated on a spinnerwith a positive-working photoresist solution (TDUR-P036PM, supra)followed by a pre-baking treatment at 80° C. for 90 seconds to give aphotoresist layer of 560 nm thickness, which was pattern-wiselight-exposed on a light-exposure machine (Model Canon FPA-3000EX3,supra) and, after a post-exposure baking treatment at 120° C. for 90seconds, subjected to a development treatment with a 2.38% by weightaqueous solution of tetramethylammonium hydroxide to give a patternedresist layer having a hole pattern of 178.1 nm diameter.

[0056] Separately, an aqueous coating solution was prepared bydissolving, in 45 g of water, 20 g of a resin mixture consisting of apolyacrylic acid resin and a poly(N-vinylpyrrolidone) resin in a weightproportion of 55:45. The resin mixture had been subjected to the test ofsolubility behavior as described before to find that the dissolving timeof the resin mixture was one second.

[0057] The above prepared patterned resist layer was coated with theaqueous coating solution followed by a heat treatment at 120° C. for 60seconds to effect thermal shrinkage. Thereafter, the coating layer waswashed with water at 23° C. to find that removal of the coating layerwas complete by washing for 60 seconds. The hole pattern diameter couldbe reduced to 157.4 nm and the cross sectional profile of the patternedresist layer was excellently orthogonal.

COMPARATIVE EXAMPLE 2

[0058] A coating solution for comparative test was prepared bydissolving 5 g of a polyvinyl alcohol resin in 95 g of water.Separately, the polyvinyl alcohol resin was subjected to the solubilitytest to find that removal of the coating layer was still incomplete evenafter 120 seconds of the washing time.

[0059] A test of coated thermal flow process was undertaken in the samemanner as in Example 5 excepting the use of the above prepared polyvinylalcohol solution as the coating solution to find that no acceptablepatterned resist layer could be obtained due to remaining residue of thecoating layer on the substrate.

COMPARATIVE EXAMPLE 3

[0060] The testing procedure was substantially the same as in Example 5except that no coating layer was formed on the patterned resist layer.The result of the test was that substantially no reduction of thepattern dimension could be obtained.

EXAMPLE 6

[0061] A semiconductor silicon wafer was spin-coated with apositive-working photoresist composition (TDUR-P036PM, supra) andsubjected to a pre-baking treatment at 80° C. for 90 seconds to form aphotoresist layer of 560 nm thickness.

[0062] The photoresist layer was pattern-wise exposed to light on alight-exposure machine (Model Canon FPA-3000EX3, supra) followed by apost-exposure baking treatment at 120° C. for 90 seconds and thensubjected to a development treatment with a 2.38% by weight aqueoussolution of tetramethylammonium hydroxide to give a patterned resistlayer having a hole pattern of 178.1 nm diameter.

[0063] Separately, a polyacrylic acid resin was subjected to thewater-solubility test by using an aqueous solution of 5.0 g of the resinin 45 g of water to find that the dissolving time was 1 second.

[0064] The hole-patterned resist layer was coated with the aqueoussolution of the polyacrylic acid resin followed by drying to form adried coating layer thereon and then subjected to a heat treatment at120° C. for 60 seconds to effect thermal shrinkage of the patternedresist layer followed by washing with water at 23° C. to find thatremoval of the coating layer was complete by washing for 1 second andthe diameter of the hole pattern was reduced to 161.4 nm.

EXAMPLE 7

[0065] A semiconductor wafer was spin-coated with the samepositive-working photoresist composition as used in Example 6 followedby a pre-baking treatment at 80° C. for 90 seconds to form a photoresistlayer of 560 nm thickness which was subjected to a pattern-wiselight-exposure in the same manner as in Example 6 followed by apost-exposure baking treatment at 120° C. for 90 seconds and then adevelopment treatment in the same manner as in Example 6 to give ahole-patterned resist layer having a hole diameter of 178.1 nm.

[0066] Separately, a water-soluble poly(N-acryloylmorpholine) resin wassubjected to the water-solubility test by using a 10% by weight aqueoussolution of the resin to find that the dissolving time of the resinouslayer was 1 second.

[0067] The above prepared hole-patterned resist layer was coated with anaqueous solution of the water-soluble resin tested above and dried toform a coating layer of the resin which was subjected to a heattreatment at 120° C. for 60 seconds to effect thermal shrinkage of thepatterned resist layer followed by removal of the coating layer bywashing with water to find that removal of the coating layer wascomplete by washing for 1 second and the diameter of the hole patternwas reduced to 166.9 nm.

EXAMPLE 8

[0068] A semiconductor silicon wafer was spin-coated with the samepositive-working photoresist composition as used in Example 6 followedby a pre-baking treatment at 80° C. for 90 seconds to form a photoresistlayer of 560 nm thickness which was pattern-wise exposed to lightfollowed by a post-exposure baking treatment and a development treatmentin the same manner as in Example 6 to form a patterned resist layerhaving a hole pattern of 180.3 nm diameter.

[0069] The thus formed patterned resist layer was coated with a 10% byweight aqueous coating solution of a water-soluble resin which was acopolymer of acrylic acid and N-vinylpyrrolidone in a copolymerizationratio of 55:45 by weight followed by a heat treatment at 120° C. for 60seconds to effect thermal shrinkage of the patterned resist layer andthen removal of the coating layer by washing with water to find thatremoval of the coating layer was complete by washing for 60 seconds andthe diameter of the hole pattern, of which the cross sectional profilewas excellently orthogonal, was reduced to 157.4 nm.

EXAMPLE 9

[0070] A semiconductor silicon wafer was spin-coated with a photoresistcomposition (TDMR-AF2000, a product by Tokyo Ohka Kogyo Co.) followed bya pre-baking treatment at 90° C. for 90 seconds to form a photoresistlayer of 1.3 μm thickness, which was pattern-wise exposed to light onthe same exposure machine as used in Example 2 followed by apost-exposure baking treatment at 110° C. for 90 seconds and developmentin the same manner as in Example 2 to give a trench-patterned resistlayer of 411.1 nm dimension.

[0071] The thus obtained trench-patterned resist layer was subjected tothe coated thermal flow process in just the same manner as in Example 8so that the dimension of the trench pattern of the resist layer, whichhad an excellently orthogonal cross sectional profile, was reduced to219.5 nm.

COMPARATIVE EXAMPLE 4

[0072] The experimental procedure was substantially the same as inExample 9 excepting for the omission of coating on the patterned resistlayer with a coating solution of a water-soluble resin. The result wasthat no reduction could be obtained in the width of the trench-patternedresist layer.

COMPARATIVE EXAMPLE 5

[0073] The experimental procedure was just the same as in Example 0.9except that the aqueous coating solution of the water-soluble resin wasreplaced with a 5% by weight aqueous solution of a polyvinyl alcohol.The result was that, after removal of the coating layer by washing withwater, trace of the coating layer could be clearly detected by visualinspection.

EXAMPLE 10

[0074] The experimental procedure was just the same as in Example 8except that the coating layer of a water-soluble resin on the patternedresist layer was formed by using a 10% by weight aqueous solution of acopolymeric resin of acrylic acid and N-acryloylmorpholine in acopolymerization ratio of 1:1 by weight. The result was that removal ofthe coating layer by washing with water was complete by washing for 1second and the hole diameter of the hole-patterned resist layer, whichhad an excellent cross sectional profile, was reduced to 159.7 nm.

EXAMPLE 11

[0075] The procedure for the formation of a hole-patterned resist layeron a semiconductor silicon wafer was just the same as in Example 1except that the hole pattern obtained had a diameter of 180.3 nm. Theprocedure of the coated thermal flow process was also just the same asin Example 1 except that the aqueous coating solution of a water-solubleresin was a 10% by weight aqueous solution of a copolymeric resin ofN-vinylpyrrolidone and N-vinylimidazolidinone in a copolymerizationratio of 1:3 by weight. The result was that removal of the coating layerwas complete by washing with water for 60 seconds and the diameter ofthe hole pattern of the resist layer, which had an excellentlyorthogonal cross sectional profile, was reduced to 170.1 nm.

EXAMPLE 12

[0076] The experimental procedure was just the same as in Example 2except that the aqueous coating solution of a water-soluble resin inExample 2 was replaced with the coating solution used in Example 10. Theresult was that the trench width of the trench-patterned resist layer,which had an excellently orthogonal cross sectional profile, was reducedto 345.3 nm.

What is claimed is:
 1. A method for reducing dimensions of a resistpattern on a substrate which comprises the steps of: (a) coating apatterned resist layer on a substrate surface with an aqueous coatingsolution comprising a water-soluble resin and a water-soluble aminecompound to form a coating layer; (b) drying the coating layer of theaqueous coating solution; (c) subjecting the dried coating layer to aheat treatment to effect thermal shrinkage of the coating layer andreduction of the distance between resist patterns; and (d) removing thecoating layer by washing with water.
 2. The method as claimed in claim 1in which the water-soluble resin is selected from the group consistingof alkyleneglycol-based polymers, cellulose-based polymers, vinylpolymers, acrylic polymers, urea-based polymers, epoxy-based polymers,melamine-based polymers and polyamide-based polymers.
 3. The method asclaimed in claim 1 in which the aqueous coating solution contains from 3to 50% by weight of the water-soluble resin.
 4. The method as claimed inclaim 1 in which the water-soluble amine compound is selected from theamine compounds having a pKa value in the range from 7.5 to 13 at 25° C.5. The method as claimed in claim 1 in which the amount of thewater-soluble amine compound contained in the aqueous coating solutionis in the range from 0.1 to 30% by weight based on the amount of thewater-soluble resin.
 6. The method as claimed in claim 1 in which thetemperature of the heat treatment in step (c) is lower than thesoftening temperature of the patterned resist layer.
 7. The method asclaimed in claim 4 in which the water-soluble amine compound ismonoethanolamine or triethanolamine.
 8. A method for reducing dimensionsof a resist pattern on a substrate surface which comprises the steps of:(a2) coating a patterned resist layer with an aqueous coating solutioncontaining a water-soluble resin, which is a copolymer of (meth)acrylicacid and an ethylenically unsaturated monomeric compound selected fromthe group consisting of N-vinylpyrrolidone, N-vinylimidazolidinone,methyl acrylate, methyl methacrylate, N,N-dimethylacrylamide,N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropylacrylamide, N-methhylacrylamide, diacetoneacrylamide,N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate,N,N-dimethylaminoethyl acrylate and N-acryloylmorpholine; (b2) dryingthe coating layer to form a dried coating layer of the water-solubleresin; (c2) subjecting the dried coating layer to a heat treatment toeffect thermal shrinkage of the coating layer and reduction ofdimensions of the resist pattern; and (d2) dissolving away the coatinglayer by washing with water.
 9. The method as claimed in claim 8 inwhich the water-soluble resin is a copolymer of (meth)acrylic acid andthe ethylenically unsaturated monomeric compound in a copolymerizationratio in the range from 4:1 to 1:1 by moles.
 10. The method as claimedin claim 8 in which the heat treatment in step (c2) is conducted at atemperature lower than the softening temperature of the patterned resistlayer.
 11. A method for reducing dimensions of a resist pattern on asubstrate surface which comprises the steps of: (a2) coating thepatterned resist layer with an aqueous coating solution containing awater-soluble resin which is a homopolymer of N-vinylpyrrolidone or acopolymer of N-vinylpyrrolidone and a comonomer which isN-vinylimidazolidinone, N-acryloylmorpholine or a combination thereof toform a coating layer of the aqueous coating solution; (b2) drying thecoating layer to form a dried coating layer of the water-soluble resin;(c2) subjecting the dried coating layer to a heat treatment to effectthermal shrinkage of the coating layer and reduction of the resistpattern dimension; and (d2) dissolving away the coating layer by washingwith water.
 12. The method as claimed in claim 11 in which thewater-soluble resin is a copolymer of N-vinylpyrrolidone andN-vinylimidazolidinone.
 13. The method as claimed in claim 12 in whichthe water-soluble resin is a copolymer of N-vinylpyrrolidone andN-vinylimidazolidinone in a copolymerization ratio in the range from 9:1to 1:9 by moles.
 14. The method as claimed in claim 11 in which thetemperature of the heat treatment in step (c2) is lower than thesoftening temperature of the patterned resist layer.
 15. An aqueouscoating solution used in the coated thermal flow process for reducing aresist pattern dimension of a patterned resist layer on a substratewhich comprises a water-soluble resin and a water-soluble aminecompound.
 16. The aqueous coating solution as claimed in claim 15 inwhich the water-soluble resin is selected from alkyleneglycol-basedpolymers, cellulosic polymers, vinyl polymers, acrylic polymers,urea-based polymers, epoxy polymers, melamine-based polymers andpolyamide polymers.
 17. The aqueous coating solution as claimed in claim15 in which the water-soluble amine compound has a pK value in the rangefrom 7.5 to
 13. 18. The aqueous coating solution as claimed in claim 15in which the water-soluble amine compound is monoethanolamine ortriethanolamine.
 19. The aqueous coating solution as claimed in claim 15in which the amount of the water-soluble amine compound is in the rangefrom 0.1 to 30% by weight based on the amount of the water-solubleresin.
 20. An aqueous coating solution of a water-soluble resin used inthe coated thermal flow process for reducing a resist pattern dimensionof a patterned resist layer on a substrate in which the water-solubleresin is a copolymer of (meth)acrylic acid and an ethylenicallyunsaturated monomeric compound selected from the group consisting ofN-vinylpyrrolidone, N-vinylimidazolidinone, methyl acrylate, methylmethacrylate, N,N-dimethylacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminopropyl acrylamide, N-methhylacrylamide,diacetoneacrylamide, N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate andN-acryloylmorpholine.
 21. The aqueous coating solution as claimed inclaim 20 in which the water-soluble resin is a copolymer of acrylic acidand N-vinylpyrrolidone.
 22. An aqueous coating solution of awater-soluble resin used in the coated thermal flow process for reducinga resist pattern dimension of a patterned resist layer on a substrate inwhich the water-soluble resin is a copolymer of N-vinylpyrrolidone andN-vinylimidazolidinone.
 23. A method for selection of a water-solubleresin used in the coated thermal flow process for reducing the patterndimension of a patterned resist layer formed on a substrate surfacecomprising the steps of forming a coating layer of a water-soluble resinon a patterned resist layer, subjecting the coating layer to a heattreatment to effect thermal shrinkage of the coating layer and reductionof the pattern dimensions and removing the coating layer by washing withwater, which comprises the steps of: (a3) forming a coating layer of thewater-soluble resin on the surface of an unpatterned but photocuredphotoresist layer on a substrate surface; (b3) subjecting the coatinglayer of the water-soluble resin at 140° C. for 60 seconds; and (c3)dissolving away the coating layer of the water-soluble resin by washingwith water at 23° C. to determine the dissolving time taken for completeremoval of the coating layer.
 24. The method as claimed in claim 23 inwhich the water-soluble resin is selected from the group consisting ofacrylic polymers, vinyl polymers, cellulose-based polymers andalkyleneglycol-based polymers.
 25. The method as claimed in claim 24 inwhich the water-soluble resin is an acrylic polymer or a vinyl polymer.26. The method as claimed in claim 25 in which the water-soluble resinis an acrylic polymer.
 27. The method as claimed in claim 23 in whichthe temperature of the heat treatment in step (b) is lower than thesoftening point of the photocured photoresist layer.